WO2015101361A1 - Procédé de production de noir de carbone blanc nanométrique par l'utilisation directe d'un gaz de carneau pour carboniser du silicate de sodium - Google Patents

Procédé de production de noir de carbone blanc nanométrique par l'utilisation directe d'un gaz de carneau pour carboniser du silicate de sodium Download PDF

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Publication number
WO2015101361A1
WO2015101361A1 PCT/CN2015/071391 CN2015071391W WO2015101361A1 WO 2015101361 A1 WO2015101361 A1 WO 2015101361A1 CN 2015071391 W CN2015071391 W CN 2015071391W WO 2015101361 A1 WO2015101361 A1 WO 2015101361A1
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WO
WIPO (PCT)
Prior art keywords
flue gas
white carbon
carbon black
water glass
solution
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Application number
PCT/CN2015/071391
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English (en)
Chinese (zh)
Inventor
郑兴才
张岩丰
方章建
陶磊明
程宇婷
Original Assignee
中盈长江国际新能源投资有限公司
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Application filed by 中盈长江国际新能源投资有限公司 filed Critical 中盈长江国际新能源投资有限公司
Publication of WO2015101361A1 publication Critical patent/WO2015101361A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention relates to a technology for utilizing boiler flue gas, in particular to a method for producing nano-scale white carbon black by directly carbonizing water glass using boiler flue gas.
  • the production process of white carbon black is divided into two types: precipitation method and gas phase method.
  • the fumed silica product is of high quality and its products are micro-nano grade and are used in many high-end products.
  • the environment in which fumed silica is produced is very harsh and the pollution is serious. Due to the high price of fumed silica, precipitated silica is generally used.
  • the precipitation method is obtained by reacting sulfuric acid or hydrochloric acid with water glass. Since the specific surface area of the white carbon black produced by the sulfuric acid method or the hydrochloric acid method is small, it is generally from 90 to 120 m 2 /g.
  • the production and use limitations are large, the market is in a low grade, the price is below 6,000 yuan / ton. Many domestic white carbon black manufacturers use this method, the output is relatively large, and some manufacturers may be eliminated in the next few years.
  • the technical problem to be solved by the present invention is to provide a method for producing nano-scale white carbon black by directly carbonizing water glass using boiler flue gas, and the white carbon black produced by the method has large specific surface area and low energy consumption, and can also make Greenhouse gas emissions from flue gases from biomass power plants are significantly reduced.
  • a method for producing nano-scale white carbon black by using boiler flue gas direct carbonized water glass which comprises the following steps:
  • Flue gas purification using flue gas generated by boiler combustion as raw material, cooling flue gas, fine purification, blasting pressure, as raw material gas for preparing white carbon black;
  • the flue gas may be a coal-fired boiler, a combustion biomass boiler, or a natural gas-fired steam boiler;
  • step 3 carbonization: the purified flue gas recovered in step 2) is passed into the sodium silicate solution obtained in step 1) to acidify and neutralize the carbon dioxide in the sodium silicate solution and the flue gas.
  • the gas pressure is 5886Pa
  • the reaction temperature is 85 ⁇ 95°C
  • the reaction time is 2.5 ⁇ 4.5h
  • a solid-liquid mixture of silica precipitate and sodium carbonate solution is formed;
  • the mass percentage concentration of the water glass solution in the step 1) is 1 to 15%.
  • the flue gas in the above solution, is cooled to below 40 ° C, and then pressurized to a gauge pressure of 5886 Pa, and after precision filtration, the flue gas contains less than 5 mg/Nm 3 of dust.
  • the reaction temperature in the step 3) is preferably 90 ° C, and the reaction time is 2.5 h, so that the sodium silicate solution and the carbon dioxide in the flue gas are sufficiently acidified and neutralized to generate as much as possible.
  • Silica precipitation and sodium carbonate solution lay the foundation for the preparation of white carbon black.
  • the chemical reaction equation is as follows:
  • Na 2 SiO 3 +CO 2 +nH 2 O Na 2 CO 3 +SiO 2 ⁇ nH 2 O
  • the above-mentioned white carbon black prepared by the method of directly producing carbonized water glass using boiler flue gas to produce nano-scale white carbon black.
  • the silica has a particle diameter of 10 to 100 nm.
  • the silica has a specific surface area of 160 to 250 m 2 /g.
  • the invention adopts carbonization (acidification) neutralization treatment of the flue gas, and the obtained white carbon black and ultrafine calcium carbonate have the advantages of:
  • the carbon dioxide in the flue gas is used as the acidification neutralization medium, and the carbon dioxide is taken to the flue gas of the power plant.
  • the raw material cost is extremely low, the source is sufficient, and carbon dioxide is used instead of sulfuric acid or hydrochloric acid, and the strong acid is excluded from the process operation.
  • a large number of interventions avoid many of the dangers and safety hazards of sulfuric acid or hydrochloric acid in transportation, storage and production, as well as environmental pollution. For example, a plant with an annual output of 30,000 tons of white carbon can save about 16,000 tons of sulfuric acid or hydrochloric acid per year.
  • the rational use of a large amount of flue gas has greatly reduced the greenhouse gas carbon dioxide gas of the power plant, effectively reducing the emission of industrial waste gas, and turning the power plant into an environmentally friendly cleaning plant.
  • a plant with an annual output of 30,000 tons of white carbon black can reduce the emission of carbon dioxide gas by about 15,000 tons per year.
  • this patent uses burning biomass boiler flue gas instead of sulfuric acid and hydrochloric acid carbonized water glass, the specific surface area of its product white carbon black is increased to 130-250m 2 /g, primary particles reach nanometer level, can be used as rubber
  • the reinforcing reinforcing agent can replace the use of some fumed silica, and the price of the product is increased to 1,200-16,000 yuan/ton.
  • the production environment is friendly and no toxic substances are discharged.
  • the production energy consumption is lower than that of the sulfuric acid or hydrochloric acid method, and the production cost is also low. Therefore, the use of flue gas carbonized water glass to produce precipitated silica has a relatively good development prospect.
  • the reaction of carbon dioxide in the flue gas with the sodium silicate solution can be made milder, the obtained white carbon black has better dispersibility, and the white carbon black has a finer particle size, so that the white carbon is made.
  • the quality of black finished products is improved.
  • the original white carbon black has a particle size of micron.
  • the direct carbonization of flue gas to form white carbon black can reach nanometer level, and the price of white carbon black finished products can be increased from less than 6,000 yuan/ton to 1,200-15,000 yuan. /Ton.
  • the waste of a biomass power plant can be processed into two industrial products: nano-silica can be used in various industries such as rubber, plastics, paint, toothpaste, catalyst, heat preservation and water quality.
  • Ultra-fine calcium carbonate is also an indispensable basic chemical raw material for the national economy. Therefore, part of the carbon dioxide gas in the flue gas of the power plant can also be used reasonably, which not only makes the power plant take a big step to the zero-row target, but also greatly reduces the production cost and energy consumption of the product, and greatly increases the The profit of power plants has significant social and economic benefits.
  • FIG. 1 is a schematic diagram of a process flow for co-production of white carbon black and ultra-fine calcium carbonate by biomass gas power plant flue gas.
  • Figure 2 is a scanning electron micrograph of the finished silica.
  • Figure 1 shows the process of co-production of white carbon black and ultra-fine calcium carbonate using biomass power plant flue gas, which includes the following steps:
  • Flue gas purification using flue gas from biomass power plant as raw material, firstly cool the flue gas to below 40 °C, then pressurize it to about 5886 Pa (gauge pressure), and after precision filtration, make the flue gas contain dust. Less than 5mg/Nm 3 ;
  • the flue gas recovered in the step 2) is passed to the sodium silicate solution obtained in the step 1), and can be carried out in a carbonization tower provided with a circulation heater externally, and the reaction temperature is set.
  • the temperature is 85 ° C -95 ° C
  • the flue gas pressure is 5886 Pa (gauge pressure)
  • the reaction time is 2.5-4.5 h, so that the sodium silicate solution or the sol and the carbon dioxide in the flue gas are fully acidified and neutralized to form two A solid-liquid mixture of silica precipitate and sodium carbonate solution.
  • step 5) Drying of white carbon black: The silica precipitate separated in step 4) is washed and dried to obtain a finished white carbon black. After testing, the quality requirements are in accordance with HG/T3061-1999 standard, and the specific surface area is 160 ⁇ 250m 2 /g.
  • the silica has a particle diameter of 10 to 100 nm.
  • the silica content of the rice hull ash determines the yield of the two finished products.
  • a biomass power plant with an annual power generation capacity of 1.2 MW can produce about 17.89 million tons of rice hull ash per year. If it contains 90% of silica, about 15,000 tons of white carbon black, the filter can be treated with ultrafine Calcium carbonate is about 6,000 tons; if it contains 60% of silica, about 1.0 million tons of white carbon black, and the filtrate treatment can obtain about 4,000 tons of ultrafine calcium carbonate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé de production de noir de carbone blanc nanométrique par l'utilisation directe d'un gaz de carneau pour carboniser du silicate de sodium. Le procédé comporte les étapes suivantes : 1.) préparation d'une solution de silicate de sodium ; 2.) purification du gaz de carneau carbonisation : introduction du gaz de carneau purifié récupéré dans l'étape 2.) dans la solution de silicate de sodium obtenue dans l'étape 1.) pour permettre une réaction d'acidification-neutralisation entre la solution de silicate de sodium et le dioxyde de carbone dans le gaz de carneau ; 4.) séparation du dioxyde de silicium : filtration des mélanges solides et liquides produits dans l'étape 3.) pour en séparer des précipités de dioxyde de silicium et la solution de carbonate de sodium ; 5.) séchage du produit noir de carbone blanc ; 6.) traitement par filtration pour donner du carbonate de calcium superfin : ajout d'eau de chaux à la solution de carbonate de sodium séparée dans l'étape 5.), puis séparation, séchage et pulvérisation pour obtenir un produit carbonate de calcium superfin. Le noir de carbone blanc produit par ledit procédé présente une grande surface spécifique, consomme peu d'énergie, et peut réduire significativement les émissions de gaz à effet de serre dans le gaz de carneau issu de centrales électriques alimentées à la biomasse.
PCT/CN2015/071391 2014-01-06 2015-01-23 Procédé de production de noir de carbone blanc nanométrique par l'utilisation directe d'un gaz de carneau pour carboniser du silicate de sodium WO2015101361A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410004639.7 2014-01-06
CN201410004639.7A CN103708475A (zh) 2014-01-06 2014-01-06 一种利用锅炉烟道气直接碳化水玻璃生产纳米级白炭黑的方法

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Cited By (8)

* Cited by examiner, † Cited by third party
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CN114105152A (zh) * 2021-11-30 2022-03-01 锦洋高新材料股份有限公司 一种纳米白炭黑的制备方法
CN114132939A (zh) * 2021-12-27 2022-03-04 江西省矿产资源保障服务中心 一种利用植硅体硅矿生产白炭黑的方法
CN114368755A (zh) * 2021-12-29 2022-04-19 四川马边龙泰磷电有限责任公司 利用黄磷废副生产沉淀白炭黑和轻质碳酸钙的工艺
CN114380296A (zh) * 2021-12-29 2022-04-22 四川马边龙泰磷电有限责任公司 一种生产沉淀白炭黑和甲酸盐的方法及装置
CN115159534A (zh) * 2022-08-15 2022-10-11 湖北新蓝天新材料股份有限公司 一种沉淀法白炭黑的表面改性方法
CN115159529A (zh) * 2022-08-15 2022-10-11 锦洋高新材料股份有限公司 一种以工业二氧化硅固废物为原料经沉淀法制备白炭黑的方法
CN115159532A (zh) * 2022-08-15 2022-10-11 锦洋高新材料股份有限公司 一种以工业二氧化硅固废物为原料制备多孔白炭黑的方法
CN115465867A (zh) * 2022-11-14 2022-12-13 国能龙源环保有限公司 一种利用废弃风电叶片制备白炭黑的方法

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CN103708475A (zh) * 2014-01-06 2014-04-09 中盈长江国际新能源投资有限公司 一种利用锅炉烟道气直接碳化水玻璃生产纳米级白炭黑的方法
CN104402004A (zh) * 2014-10-24 2015-03-11 山西玉竹活性石灰制造有限公司 一种工业水玻璃并流碳分生产白炭黑的制备方法
CN114988418A (zh) * 2021-03-02 2022-09-02 香港理工大学 一种利用废弃混凝土砂粉制备纳米二氧化硅的方法

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CN101898776A (zh) * 2009-05-27 2010-12-01 北京紫光英力化工技术有限公司 一种联产超微细白炭黑和碳酸钙的新工艺
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114105152A (zh) * 2021-11-30 2022-03-01 锦洋高新材料股份有限公司 一种纳米白炭黑的制备方法
CN114132939A (zh) * 2021-12-27 2022-03-04 江西省矿产资源保障服务中心 一种利用植硅体硅矿生产白炭黑的方法
CN114368755A (zh) * 2021-12-29 2022-04-19 四川马边龙泰磷电有限责任公司 利用黄磷废副生产沉淀白炭黑和轻质碳酸钙的工艺
CN114380296A (zh) * 2021-12-29 2022-04-22 四川马边龙泰磷电有限责任公司 一种生产沉淀白炭黑和甲酸盐的方法及装置
CN114380296B (zh) * 2021-12-29 2023-09-08 四川马边龙泰磷电有限责任公司 一种生产沉淀白炭黑和甲酸盐的方法及装置
CN114368755B (zh) * 2021-12-29 2024-04-05 四川马边龙泰磷电有限责任公司 利用黄磷废副生产沉淀白炭黑和轻质碳酸钙的工艺
CN115159534A (zh) * 2022-08-15 2022-10-11 湖北新蓝天新材料股份有限公司 一种沉淀法白炭黑的表面改性方法
CN115159529A (zh) * 2022-08-15 2022-10-11 锦洋高新材料股份有限公司 一种以工业二氧化硅固废物为原料经沉淀法制备白炭黑的方法
CN115159532A (zh) * 2022-08-15 2022-10-11 锦洋高新材料股份有限公司 一种以工业二氧化硅固废物为原料制备多孔白炭黑的方法
CN115465867A (zh) * 2022-11-14 2022-12-13 国能龙源环保有限公司 一种利用废弃风电叶片制备白炭黑的方法
CN115465867B (zh) * 2022-11-14 2023-02-21 国能龙源环保有限公司 一种利用废弃风电叶片制备白炭黑的方法

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